Starting from 4-bromobenzaldehyde or 1,4-benzenedicarboxaldehyde, two new poly(p-phenylenevinylene) derivatives P1 and P2 were synthesized by a five-step synthetic route. These fully conjugated polymers contain 1 or 2 oxadiazole rings and 3 or 4 vinylene bonds per repeat unit for P1 and P2, respectively, and were amorphous and soluble in common organic solvents. The Tg values were 28 °C for P1 and 57 °C for P2. The polymers emitted greenish-blue light in solution with photoluminescence (PL) emission maximum at 487−511 nm and yellowish-green light with PL emission maximum at 515−558 nm in thin films. Electroluminescence (EL) was achieved from single-layer LEDs of polymer P1 with the configuration ITO/PEDOT/P1/Al with voltage-tunable EL colors from 558 nm (9 V) to 527 nm (16 V). The observed EL spectral blue shift with increasing voltage is a result of conformational changes of the polymer backbone with increase in temperature, as evidenced from the absorption and PL spectra changes upon annealing of P1 thi...